JPH04116544A - Production of coating liquid - Google Patents

Abstract

PURPOSE:To obviate the presence of a nonuniform gel or undissolved water-soluble polymer in a coating layer by adding water kept at >=5 and <=35 deg.C as a solvent to the water-soluble polymer and dissolving the polymer at the time of dissolving the water-soluble polymer. CONSTITUTION:The water kept at >=5 and <=35 deg.C is added as the solvent to the water-soluble polymer and the polymer is dissolved at the time of dissolving the water-soluble polymer in the case of production of the coating liquid contg. the water-soluble polymer which is reversibly sol-gel converted by heating- cooling of the aq. soln. Sufficiently satisfactory uniformity is obtd. even with a photographic material for which the uniformity of a coated surface state is extremely highly demanded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a coating liquid containing a water-soluble polymer.

In particular, the present invention relates to a method for producing a coating liquid containing a water-soluble polymer for image formation with improved image unevenness.

(Prior art) In order to uniformly apply a coating liquid onto a support, a coating device,
Various improvements have been made to drying methods, coating liquid formulations, etc.

Among these methods, a method is commonly used in the photographic industry and the like to form a coating layer on a support using a water-soluble polymer that undergoes reversible sol-gel conversion by heating and cooling an aqueous solution as a binder.

However, in a coating layer coated with a coating solution containing the water-soluble polymer described above, non-uniform gels of different sizes or undissolved water-soluble polymers tend to exist, leading to a decrease in the quality of the target product. Particularly when the object is a photographic element (photosensitive material or image-receiving material), the problem of inconsistent photographic quality arises. For example, if an uneven gel or unmelted water-soluble polymer is present in an image-receiving material (also called a dye-fixing material) used to transfer image-forming components from a photosensitive material to obtain an image, the image-forming components may The diffusion distance varies from place to place, and there are parts where the photosensitive material and image-receiving material do not come into contact, resulting in uneven images.
Only low quality images will be obtained.

In particular, natural polymeric polysaccharides (e.g., natural polymeric polysaccharides derived from red algae such as carrageenans and farcellan, dulan gum, etc.) are used as water-soluble polymers that undergo reversible sol-gel transformation by heating and cooling an aqueous solution. When using the obtained natural polymeric polysaccharide), there is a problem that these powders dissolve in water and tend to form lumps called lumps, lumps, and mako, which tends to cause uneven application. Moreover, in order to eliminate the mamako once formed, a long-time dissolution process at high temperature is required.

Furthermore, such natural polymeric polysaccharides have poor solubility in the regenerated gel in the coating solution, resulting in formation of non-uniform gel in the coating solution, resulting in a problem of deterioration of coating surface quality.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing a coating liquid for obtaining a coated surface without the presence of non-uniform gel or undissolved water-soluble polymer in the coating layer. That is.

(Means for Solving the Problems) The above problems are as follows: (1) In the process of manufacturing a coating solution containing a water-soluble polymer that undergoes reversible sol-gel conversion by heating and cooling an aqueous solution, the water-soluble polymer is dissolved. When the temperature is 5°C or higher, 35
A method for producing a coating solution, characterized by adding and dissolving water at a temperature below °C as a solvent; (2) producing a coating solution containing a water-soluble polymer that undergoes reversible sol-gel conversion by heating and cooling the aqueous solution; During the entire process up to coating on the support, the temperature of the wall surface in contact with the coating solution should be kept at or above "gelling temperature (°C) of the coating solution -10°C" [gelling temperature (°C) + 40°C]. A method for producing a coating solution, characterized in that the water-soluble polymer is a natural polymeric polysaccharide selected from agar, casobara glutenan, lambda carrageenan, iota carrageenan, and furseleran. The problem has been solved by the method for manufacturing a coating liquid described in (1) or (2) above.

Natural polymeric substances such as gelatin are used as water-soluble polymers that undergo reversible sol-gel conversion by heating and cooling an aqueous solution used in the present invention.

As the gelatin, any of acid-treated gelatin, lime-treated gelatin, enzyme-treated gelatin, etc. can be used.
Also, skin gelatin or bone (ossein) gelatin may be used.

-Lime-treated ossein gelatin is used for boat fishing. Lime-processed ossein gelatin that has undergone a calcium removal process can also be used.

Furthermore, the effects of the present invention are particularly pronounced when a natural high-molecular polysaccharide is used as the water-soluble polymer. As a natural polymeric polysaccharide, “Food Industry J Volume 31 (
198B) Listed in Table 1 on page 21 are the natural polymers of class 1 obtained by extraction and purification from red algae.

Natural polymers derived from red algae include various types of polyIi.
It is often a mixture of type i. In the present invention, this mixture can be used as it is, or it can be used alone with even higher purity.

Among the natural high-molecular polysaccharides derived from red algae, those particularly suitable for coating photographic elements include agar, kappa carrageenan, lambda carrageenan, iota carrageenan, farseleran and the like. These substances are also available as commercial products. For example, Chikara and Parr force uginane are available as Tight-gelling agent NK-4 manufactured by Taito Co., Ltd., and lambda carrageenan mixed with a trace amount of Kanoper carrageenan are available as Tight-gelling agent MV manufactured by Taito Co., Ltd. can.

In addition, natural polymer polyols obtained by fermentation, such as duran gum (manufactured by Dainippon Pharmaceutical Co., Ltd.: Kelcogel), can also be used.

When these water-soluble polymers are dissolved, hot water is usually used to speed up the dissolution. However, if high-temperature water is added at the initial stage, so-called "mamako" is likely to occur, which will cause serious damage to the quality of the target product.

According to the present invention, the generation of mako can be prevented by controlling the temperature of the water added during dissolution of the water-soluble polymer to 35° C. or lower, more preferably 30° C. or lower.

As a result, even in the case of photographic materials, which require very high uniformity of the coated surface, sufficiently satisfactory uniformity was obtained.

However, since water is added and dissolved by heating, water at a temperature of 5° C. or higher is preferable in order to save cost and time.

More preferably, water has a temperature of 10°C or higher.

In the present invention, preferably, the water-soluble polymer as described above is dispersed in a hydrophilic organic solvent that does not substantially dissolve the water-soluble polymer, and then water is added to dissolve the water-soluble polymer, or the water-soluble polymer is dissolved in the hydrophilic organic solvent. A solution is prepared by dissolving the water-soluble polymer in a mixed solution of a water-soluble organic solvent and water (this is referred to as a solution of the water-soluble polymer of the present invention), and the resulting 78 solution can be used directly as a coating solution, or it can be used as an aqueous solution for forming other binders. It can be used as a coating liquid by mixing it with an aqueous solution of a polymer.

The general method of using the water-soluble polymer coating solution obtained in the present invention is to apply it onto a support while keeping the solution temperature higher than the gelling temperature of the coating solution, and then cool it to below the gelling temperature. , to obtain a uniform coating layer by gelation.

However, even though the temperature of the coating liquid is maintained above the gelling temperature, gels of non-uniform size may appear on the coating layer. As a result of intensive investigation into the cause of this problem, the inventor of the present invention found that the temperature of the wall surface of the manufacturing equipment (e.g. liquid preparation equipment, liquid feeding equipment, coating equipment) that comes into contact with the coating liquid during the dissolution process is related to the frequency of occurrence of this problem. Ta.

That is, when the part of these manufacturing apparatuses that comes into contact with the coating liquid is at a gelation temperature (°C) of -10°C or lower, the coating liquid locally gels in that part, producing large and small gels. Furthermore, it has become clear that the generated gel is very slow to re-dissolve and remains until it is applied, causing problems.

A specific method to solve this problem is to prepare the coating solution, transport the solution, and keep the coating equipment warm (10°C below the gelling temperature) in all processes from manufacturing the coating solution to coating it on the support. There is a method of keeping the temperature higher than the specified temperature.

In addition, it is effective to raise the dissolution temperature in order to perform dissolution quickly, but in order to avoid a cooling process later, it is necessary to ensure that the part of the dissolution process equipment that comes into contact with the coating liquid has a gelation temperature <"c". > It is better to keep the temperature below +40°C.

In other words, in the entire process from manufacturing the coating solution to coating it on the support, the temperature of the wall surface of the device that comes into contact with the coating solution throughout the entire process is set to 10 degrees below the gelling temperature of the coating solution (°C).
℃-1 or higher, the gelling temperature of the coating solution plus 40℃J
Below, it is recommended that the gelling temperature of the coating liquid (℃) be greater than or equal to the gelling temperature of the coating liquid plus 35℃.
By keeping the temperature below ℃j, a coating solution can be rapidly produced without the presence of non-uniform gel in the coating layer.

The gelation temperature mentioned here refers to the temperature at which a solution of a water-soluble polymer that undergoes reversible sol-gel conversion by heating and cooling is gradually cooled (-]'c 7m1n) until the solution viscosity reaches 1000 cp.
Indicate the temperature reached.

In the present invention, the solution of the water-soluble polymer of the present invention can be used directly or as a solution of other water-soluble polymer for forming a binder.
e. (for example, gelatin water iti'a prepared by a method different from that of the present invention) to form a coating solution, which is coated on a suitable support.

There are no particular limitations on the coating method used in the present invention, and conventionally known dip coating methods, roller coating methods, reverse roll coating methods, air knife coating methods, doctor blade coating methods, spray coating methods, bead coating methods, extrusion Methods and apparatuses for coating methods, trench flow coating methods, curtain coating methods, etc. can be used.

By cooling the coating layer after coating, the water-soluble polymer solution is gelled, and then the coating layer can be obtained by drying.

The coating method of the present invention can be applied to materials for various uses using water-soluble polymers as binders. Examples include inkjet recording paper, thermal paper,
Examples include thermal transfer paper, clinical test analysis elements, plotter paper, developing elements for autoradiography, optical filters, silver halide photosensitive materials, and image-receiving materials.

Among these, silver halide light-sensitive materials and image-receiving materials (sometimes called dye-fixing materials) that transfer image-forming substances diffused from silver halide light-sensitive materials in diffusion transfer systems can best utilize the features of the present invention. So,
This will be explained below.

A silver halide photosensitive material is a material containing silver halide as a photosensitive element. The coating method of the present invention includes the photosensitive layer and other constituent layers (overcoat layer, intermediate layer, undercoat layer, antihalation layer, filter layer, backing layer, antistatic layer, diffusible dye-providing compound layer, water absorbing layer, etc.) of the photosensitive material. layer, processing agent supply layer, energized heat generating layer, etc.).

The coating method of the present invention also applies to the image-receiving layer and other constituent layers of the image-receiving material (overcoat layer, intermediate layer, undercoat layer, backing layer, current heating layer, water absorption layer, white reflective layer, neutralization layer, timing layer, etc.). ) can be used for coating.

In the photographic emulsion layer of the photographic photosensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

Silver halide grains in photographic emulsions may be so-called regular grains with regular crystal structures such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as spherical shapes. , one with crystal defects such as twin planes, or a composite form thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Phys
ique PhotographiquePaul M
ontel, I 967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi
n.

Photographic Emulsion Che
mistry (Focal Press1966),
"Production and Coating of Photographic Emulsions" by Zelikman et al., published by J1 Focal Press (V.L., Zelikman et al., M.
making and coating photo
graphic Emulsion Focal P
(Ress, 1964). That is, acidic method, neutral method,
Any method such as the ammonia method may be used, and methods for reacting soluble silver salts with soluble halogen salts include one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which Ag in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) Volume 6, pp. 159-165 (1962) i-Journal op Photographic Science (Journalo
f Photographic 5science),
12 t', pp. 242-251 (1964), U.S. Patent No. 3.655,394 and British Patent No. 1.4.
No. 13,748.

Regarding monodispersed emulsions, JP-A No. 48-8600,
No. 51-39027, No. 51-83097, No. 53
-137133, 54-48521, 54-9
No. 9419, No. 5B-37635, No. 5B-4993
No. 8, Special Publication No. 4711386, U.S. Patent Box 3.655
．． No. 394 and British Patent No. 1,413,748.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Cleve's Theory and Practice of Photography.
y Theory and Practice (193
0) ).

131 pages; Gatoff, Photographic Science
and Engineering Link (Cutoff.

Photographic 5science and
Engineering) + Volume 14, 248-257
Page (1970); U.S. Patent Box 4,434,226;
4.414,310, 4,433.048, 4,439.520 and British Patent No. 2,112.1
It can be easily prepared by the method described in No. 57, etc. When tabular grains are used, the covering power increases;
Advantages include increased color enhancement efficiency with sensitizing dyes, and are detailed in the above-cited U.S. Pat. No. 4,434,226.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1.027.1.
No. 46, U.S. Patent Box 3,505.068, U.S. Patent Box 4,44
4.877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Patent Box 4,094.
．． No. 684, No. 4,142.900, No. 4,459,
No. 353, British Patent No. 2.038,792, U.S. Patent Box No. 4.349.622, No. 4,395,478, No. 4°433.501, No. 4,463.087, No. 3
．． It is disclosed in No. 656.962, No. 3,852,067, and Japanese Patent Application Laid-open No. 5!1162540.

Also, mixtures of particles of various crystal forms may be used.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further modification, the ripening agent can also be introduced independently at the halide salt and silver salt addition steps.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Patent Nos. 2,222,264 and 2,44.
8.534 and 3,320,069. Also, U.S. Patent Box No. 3,271.157;
Commonly used thioether ripening agents such as those described in No. 574,628 and No. 3,737,313 can also be used. Alternatively, 1,000-ion compounds as taught in JP-A-82408 and JP-A-53-144319 can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. For US patents 2,
No. 448,060, No. 2,628,167, No. 3,7
Copper, iridium, lead, as described in 37°313, 3,772.031, and Research Disclosure, Vol.
The properties of silver halide can be controlled by the presence of compounds such as bismuth, cadmium, zinc (chalcogen compounds such as sulfur, selenium, and tellurium), gold, and compounds of Group I noble metals during the silver halide precipitation process.

As described in Japanese Patent Publication No. 5B-1410, by Moisar et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions produce grains during the precipitation process. can be sensitized by internal reduction.

Silver halide emulsions are usually chemically sensitized.

Chemical sensitization is described by T. H. James,
The Photographic Ink Process, 4th edition, Macmillan Publishing, 1977, (T. H. James, The
Theory of the Photographic
Process, 4th ed, Macmill
an.

1977), pp. 6'1-76, or as described in Research Disclosure, Vol. 120, April 1974, 12008.
;Research Disclosure, Volume 34, 1975 6
U.S. Pat.
．． No. 857711, No. 3.901.714, No. 4.2
pAg 5-10, pH 5-8 and temperature 30-80° C.
This can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, or a combination of these sensitizers.

Chemical sensitization is optimally carried out in the presence of gold compounds and thiocyanate compounds, as well as sulfur-containing compounds or compounds described in U.S. Pat. It is carried out in the presence of sulfur-containing compounds such as hypo, thiourea compounds, and rhodanine compounds. Chemical sensitization can also be carried out in the presence of chemical sensitization aids.

The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat.
No. 3.554757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, 138-143.
It is written on the page. In addition to or in place of chemical sensitization, U.S. Pat.
Reduction sensitization can be performed, for example, using hydrogen, as described in US Patent No. 2,518, US Pat.
No. 698, No. 2,743゜182 and No. 2,743
, 183, using reducing agents such as stannous chloride, thiourea dioxide, polyamines, and low pAg (e.g. less than 5) and/or high pH.
(e.g. greater than 8) can be reduced sensitized by treatment. Also, U.S. Patent No. 3.917.485 and U.S. Pat.
Color sensitization can also be improved by the chemical sensitization method described in No. 966.476.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine A henzindolenine nucleus, an indole nucleus, a henzoxadol nucleus, a naphthoxazole nucleus, a henzothiazole nucleus, a naphthothiazole nucleus, a henzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heteroartic ring nucleus such as a 4-dione nucleus, a thiacylysia 2.4-';on nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilhensen compound with a nitrogen-containing heteroartic ring group (e.g., U.S. Pat. No. 2.933.390, U.S. Pat. No. 3.635.7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615.613, 3.
No. 615.641, No. 3,617,295, No. 3.
635. The combinations described in No. 721 are particularly useful.

In the present invention, various compounds are used in combination with the compound of general formula (I) for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of photosensitive materials, or stabilizing photographic performance. Compounds may be included. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorohenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptohenzothiazoles, mercaptohenzimidazoles, mercaptothiadiazoles. , aminotriazoles, hencytriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1
, 3, 3a, 7) tetraazaindenes), pentaazaindenes, etc.; many known as antifoggants or stabilizers such as henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. compounds can be added.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., using various synthetic hydrophilic polymeric materials such as single or copolymers. I can do it.

As for gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Phot, Japan), k 1
6, p. 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the hack layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxy-1,35
-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, 2-bis(vinylsulfonylacetamido)ethane or vinyl compounds with a vinylsulfonyl group in the side chain) Polymers, etc.) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) also have a fast curing speed. Are better.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α - Paper coated or laminated with an olefinic polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. Research Disclosure, 17123 (1)
(July 978), or by utilizing the black-forming couplers described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136, etc. Therefore, the present invention can also be applied to black and white photosensitive materials such as those for XvA. Plate-making films such as lithography film or scanner film, XG film for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, C0M or regular microfilm, silver salt diffusion transfer type photosensitive materials and prints. The present invention can also be applied to out-type photosensitive materials.

When the present invention is applied to a coupler-type color photosensitive material, various color couplers can be used. Here, the term "color coupler" refers to a compound that can generate a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone, etc. Alternatively, there are pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 17643 (197
8) Section Vll-D and 18717 (19
It is described in the patent cited in November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent coupler substituted with a campling leaving group is preferable to a four-equivalent coupler in which the campling active position is a hydrogen atom, since the amount of coated silver can be reduced. Further, a coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2.875.057 and No. 3
In the present invention, it is preferable to use two-equivalent yellow couplers, as described in U.S. Pat. No. 3,408,194, U.S. Pat.
No. 3,933,501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 58-10739.

U.S. Patent No. 4.401.752, U.S. Patent No. 4,326.0
No. 24, RD18053 (April 1979) British Patent No. 1,425,020, West German Application No. 2.219,
No. 917, No. 2,261,361, No. 2,329
Typical examples include the nitrogen atom separation type yellow couplers described in , No. 587 and No. 2, 433.812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-henzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. A 5-pyrazolone coupler in which the 3-position is substituted with a fluoramino group or an asolamino group is preferable from the viewpoint of the hue and color density of the coloring dye, and a typical example thereof is as described in U.S. Pat. No. 2゜3
No. 43.703, No. 2,600,788, No. 2,
No. 908,573, No. 3,062,653, No. 3
, No. 152,896 and No. 3936.015. As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the leaving group in U.S. Pat.
Particularly preferred are the arylthio groups described in No. 897.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
061,432, preferably pyrazolo(5,1-C)(1,2,4) triazoles as described in U.S. Pat. No. 3,725,067, Research Disclosure 24220
(June 1984) and JP-A No. 60-33552, and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659. . Imidazo (1,2-bl pyrazoles) described in U.S. Pat. No. 4,500.630 are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness; The pyrazolo[1,5-b)(1,2°4] triazoles described are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293 and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
No. 01,171, No. 2.772,162, No. 2,
No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, exemplified by U.S. Pat. No. 3.77.
Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 2,002, US Pat.
No. 58,308, same No. 4. 126. No. 396, No. 4,334.011, No. 4.327.173, West German Patent Publication No. 3. 329. 729 and European Patent No. 121.365, and U.S. Pat.
No. 446,622, No. 4,333,999, No. 4
．． These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in Japanese Patent No. 451.559 and No. 4,427,767. Special application 193605゜59-264
Cyan couplers in which naphthol is substituted with a sulfonamide group, an amide group, etc. at the 5-position described in No. 277 and No. 59-268135 also have excellent fastness of colored images and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing. U.S. Patent No. 4.163670 and Japanese Patent Publication No. 1983
-39413, etc. or U.S. Pat. No. 4,004,929, U.S. Pat.
Typical examples include the magenta-colored cyan couplers described in No. 138258 and British Patent No. 1,146.368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570.
Also, European Patent Box No. 96゜570 and West German Application No. 3
．． No. 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173, U.S. Pat. No. 4,367.2
No. 82, Japanese Patent Application No. 175041, and No. 60-11
3596.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It is also possible to introduce more than one.

The coupler can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions.

Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion,
Further, if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids 1! (Trifel phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenine phosphonate, etc.), benzoic acid ester w4 (2-ethylhexyl phenine phosphonate, etc.), Shade, dodecylhensoate, 2-ethylhexyl-p-hydroxyhenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4- tert-amylphenol, etc.)
, aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-diptyl-2-butoxy-5-tert-octylaniline, etc.), Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

Various photographic additives that can be used in the present invention are described, for example, in the aforementioned Research Disclosure No. 17643, pages 23-28 and Research Disclosure No. 18716, pages 648-651. The types of these additives and their detailed descriptions are shown below. :Additive type RD1764
3 RD187161 Chemical sensitizer page 23 6
Page 48 right column 2 Sensitivity increasing agent Same as above 3 Spectral sensitizer, pages 23-24 Page 648 right column ~ Super sensitizer 4 Brightener 5 Anti-fogging agent and stabilizer 6 Light absorber, filter dye Ultraviolet absorption Agent 7 Anti-stain agent 8 Dye image stabilizer 9 Hardener 10 Binder 11 Plasticizer, lubricant 12 Coating agent, surfactant 13 Anti-static agent Page 649 Right column 24 Pages 24-25 Page 649 Right column 25 - Page 26 Page 649 Right Column - Page 650 Left Column Page 25 Page Right Page 650 Left to Right Column Page 25 Page 26 Page 26 Page 27 Pages 26 to 27 Page 651 Left Column Page 650 Page Right Column Same as Above Page 27 Same as Above of the Present Invention For photographic processing of light-sensitive materials, any known method can be used, and known processing solutions can be used. In addition, the processing temperature is usually from 18°C to 50°C.
selected between ℃ but below 18℃ or 50℃
The temperature may exceed . Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g. 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-Nβ-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methanesulfamide ethylaniline, 4-amino-3
-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, F. A. Meson, "Photographic Ink Processing Chemistry", published by Focal Press (1
966), pages 226-229, U.S. Patent No. 2,193,
No. 015, No. 2,592,364, Japanese Unexamined Patent Publication No. 48-64
Those described in No. 933 may also be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants other than the compounds of this invention. , an antifoggant, and the like. Also, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development inhibitors such as polyethylene glycol, quaternary ammonium salts, and amines, color-forming power pullers, and competitive couplers. , fogging agents such as sodium polonitride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, U.S. Pat. No. 4,083,
The polycarboxylic acid chelate described in No. 723, the antioxidant described in OLS No. 2,622.950, and the like may be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (I), cobalt (■), chromium (■), and copper (n), peracids, quinones, and nitro-no compounds. For example, ferricyanide, dichromate, organic complex salts of iron (I or Ill), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-
For example, aminopolycarboxylic acids such as nortetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Among these, potassium ferricyanide, iron (I[l) sodium ethylenediaminetetraacetate, and ammonium iron (I[[) ethylenediaminetetraacetate] are particularly useful. Ethylenediaminetetraacetic acid iron(1) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3,042.52
No. 0, No. 3,241,966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A-53-65732, various additives can also be added.

The washing process is sometimes carried out in one tank, but in many cases it is carried out in two tanks.
It is carried out using a multi-stage countercurrent water washing method with more than one tank.

The amount of water in the washing process can be set arbitrarily depending on the type and purpose of the color photosensitive material, but for example, as described in Journal of Motion Picture and Television Engineering, Vol. 64, pp. 248-253 (May 1955).
“WaterFlow Rates in Immersion Enjoying Op Motion Picture Film” (Month issue)
Immersion-Washing of M
otionPicture Fil+w, S, R, Go
ldwasser).

In order to reduce the amount of water used for washing, the growth of bacteria and mold becomes a problem.
Washing water with reduced calcium and magnesium content, bactericides and fungicides, such as those described in the Journal of Antibacterial and Antifungal Agents (J, Antibact, Antifu)
g, Agents) v o I, 11, N115
, p. 207-223 (1983) and the compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi). In addition, chelating agents such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can also be added as water softeners.

When reducing the amount of washing water, the amount of water used is usually 100 Jd to 2000 d per rrf of color photosensitive material, and a range of 200 d to 1000 d is particularly preferably used in order to achieve both color image stability and water saving effect. .

The pH in the water washing step is usually in the range of 5 to 9.

When the light-sensitive material of the present invention is applied to color diffusion transfer photography, peel-off (beer-apart) type or Japanese Patent Publication No. 46
-16356, No. 48-33697, JP-A No. 5 (1973)
- integrated type as described in No. 13040 and British Patent No. 1,330,524;
It is possible to adopt a structure of a film unit that does not require peeling as described in JP-A-57-119345.

In either type of former, the use of a polymeric acid layer protected by a neutralized timing layer is advantageous in increasing the processing temperature tolerance. When used in color diffusion transfer photography, it may be added to any layer in the sensitive material, or it may be sealed in a processing solution container as a developer component.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to different spectral regions are used in combination. Examples include a 3N combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can have various arrangement orders known for color photosensitive materials.

Further, each of these photosensitive layers may be divided into two or more layers as necessary.

When the photosensitive material of the present invention is used as a heat-developable photosensitive material, an organic metal salt can be used together with the photosensitive silver halide as an oxidizing agent.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the silver salt oxidizing agent described above include U.S. Pat.
There are hensitriazoles, fatty acids and other compounds described in 2-53 Ran. Furthermore, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235, and JP-A-61-249044
Also useful is acetylene silver, described in No. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 to 10 g/silver equivalent.
n( is appropriate.

As the reducing agent used in the photothermographic material, those known in the field of photothermographic materials can be used. Further, a dye-donating compound having reducing properties, which will be described later, is also included (in this case, other reducing agents can also be used in combination). Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in heat-developable photosensitive materials and color diffusion transfer methods include U.S. Pat. No. 4,500°626, No. 4
Columns 9 to 50, No. 4,483,914, No. 30 to 31
! M, 4,330.617, 4.590.1
No. 52, JP-A No. 60140335, Nos. (17) to (1)
8) page, No. 57-40245, No. 56-138736
No. 59-178458, No. 59-53831,
59-182449, 59-182450, 60-119555, 60-128436 to 60-128439, 60198540, 6 (1-181742, 61-259253, 62-244044, 62-131253 to 62-131256, European Patent No. 220.746
There are reducing agents and reducing agent precursors described in pages 78 to 96 of No. A2.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent is optionally added to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of precursors can be used.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).

Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminephenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-51-110827, and dye-donating compounds with diffusion resistance and reducing properties described below.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

A compound that produces or releases a mobile dye in response to or inversely when silver ions are reduced to silver in heat-developable color diffusion transfer or conventional color diffusion transfer. , that is, a dye-donating compound is used.

Examples of dye-donating compounds include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler is also a 4-equivalent coupler,
A 2-equivalent coupler may also be used.

Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. This diffusion-resistant group may form a polymer chain.

Specific examples of color developers and couplers are given by James, “
The Theory of the Photographic Process” 4th edition (T.

H. James “The Theory of th
e Photographic Process'')29
1-334 pages, and 354-361 pages, Japanese Patent Application Laid-open No. 1983-
No. 123533, No. 58-149046, No. 58-1
No. 49047, No. 59-111148, No. 59-12
No. 4399, No. 59-174835, No. 59-231
No. 539, No. 59-231540, No. 60-2950
No. 60-2951, No. 60-14242, No. 6
It is described in detail in No. 0-23474, No. 60-66249, etc.

Further, as another example of the dye-providing compound, there can be mentioned a compound having the ability to release or diffuse a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (Ll).

(Dye-Y), -Z (Ll)I) ye represents a dye group, a dye group temporarily shortened or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image-forming Correspondingly or inversely to the photosensitive silver salt having a latent image, a difference is caused in the diffusivity of the compound represented by (Dye-Y)fi-Z, or [)ye is released, and the released Represents a group having a property that causes a difference in diffusivity between pye and (Dy e-Y) , -Z, n represents 1 or 2, and when n is 2, two Dy
e-Y may be the same or different and may be %s.

Specific examples of the dye-providing compound represented by the general formula (Ll) include the following compounds (1) to (2).

Note that ■ to ■ below are those that form a diffusive dye image (positive dye image) in reverse response to silver halide development.
(2) and (2) form a diffusive dye image (negative dye image) in response to silver halide development.

■U.S. Patent No. 3,134,764, U.S. Patent No. 3°362.
No. 819, No. 3,597,200, No. 3.544
．． 545, No. 3,482,972, etc., a dye developer in which a hydroquinone developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

■As described in US Pat. No. 4,503,137, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used. Examples include U.S. Patent Box 3,980.
Compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions, as described in U.S. Patent Box 4,199.3
Examples include compounds that release a diffusible dye through an intramolecular rewinding reaction of an isoxacilone ring, as described in No. 54 and the like.

■US Patent No. 4,559,290, European Patent No. 220
, 746A2, U.S. Pat. Chemical compounds can also be used.

Examples include U.S. Patent No. 4,139,389, U.S. Pat. Compound releasing diffusible dye by nucleophilic substitution reaction, U.S. Patent No. 4,232,107, JP-A-5
No. 9-101649, No. 61-88257, RD24
025 (1984) etc., a compound which releases a diffusible dye by an electron transfer reaction of the separated meat after being reduced, West German Patent No. 3.008.588A, JP-A-1988-
No. 142530, U.S. Pat. No. 4,343.893, U.S. Pat. No. 4,619,884, and other compounds whose single bonds are cleaved to release a diffusible dye after reduction; U.S. Pat. No. 4,450; Examples include nitro compounds that release diffusible dyes after accepting electrons, such as those described in US Pat. No. 4,609,610, which release diffusible dyes after accepting electrons, etc.

Also, more preferably, European Patent No. 220.7
No. 46A2, Publication Axis 87-6199, U.S. Pat.
No. 783.396, JP-A-63201653, JP-A No. 61
201654 etc., N-X bond (X
represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, and a compound that has SOz -X (x is the same as the above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 1983-106B85. , a compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule, described in JP-A-63-271344, JP-A-63-27134
Compounds described in No. 1 that have a c-x' bond (X' is synonymous with X or represents -SO□) and an electron-withdrawing group in one molecule can be mentioned. Also, patent application No. 61-319989
Compounds described in No. 62-320771, in which the single bond is cleaved after reduction due to a π bond conjugated with an electron-accepting group and release a diffusible dye, can also be used.

Among these, compounds having an N-X bond and an electron-withdrawing group in the -molecule are particularly preferred. A specific example is European Patent No. 22
Compounds (1) to (3), (7) to (10) described in 0,746A2 or U.S. Pat. No. 4,783,396
, (12), (13) (15), (23) to (26),
(31), (32), (35), (36), (40),
(41), (44), (53) to (59), (64),
(70), compound (11) of published branch axis 87-6199 ~
(23) etc.

■A compound that is a coupler that has a diffusible dye as a leaving group and releases the diffusible dye upon reaction with the oxidized form of a reducing agent (D
DR coupler). Specifically, British Patent No. 1,330.
No. 524, Japanese Patent Publication No. 48-39.165, U.S. Patent No. 3
．． There are those described in No. 443,940, No. 4,474,867, No. 4,483.914, etc.

■Reducing to silver halide or organic silver salt,
A compound that releases a diffusible dye upon reduction of its partner (DR
R compound). This compound is preferable because it does not require the use of other reducing agents and does not cause the problem of image staining due to oxidative decomposition products of the reducing agent.

Typical examples are U.S. Patent No. 3,928,312, U.S. Pat.
No. 59-69839, No. 533819, No. 51-1
No. 04,343, RD17465, U.S. Patent No. 3.7
No. 25,062, No. 3,728,113, No. 3,
No. 443,939, JP-A No. 58-116.537, JP-A-57179840, and U.S. Pat. No. 4,500,626. Specific examples of DRR compounds include columns 22 to 4 of the aforementioned U.S. Pat. No. 4,500.626.
Among them, compounds (1) to (3) and (10) described in the above-mentioned U.S. patent can be mentioned.
~(13), (16) ~(19), (28) ~(30)
, (33) to (35), (38) to (40), (42)
~(64) is preferred. Also, U.S. Patent No. 4,639゜4
Compounds described in No. 08 No. 37-39 Ifi are also useful.

In addition, as dye-donating compounds other than the couplers and general formula (LI) mentioned above, dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Magazine 1978
May issue, pp. 54-58), azo dyes used in heat-developable silver dye bleaching methods (U.S. Pat. No. 4,235,957,
Research Disclosure magazine, April 1976 issue,
30-32), leuco dye (U.S. Pat. No. 3,985)
, No. 565, No. 4,022,617, etc.) can also be used.

In a heat-developable photosensitive material, a compound that activates development and stabilizes the image at the same time can be used in the photosensitive material.

Specific compounds preferably used are described in columns 51-52 of U.S. Pat. No. 4,500,626.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in US Pat. No. 4,500,626, No. 57M can also be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, pages (25) and 62 of JP-A-62-253159.
-245253, etc.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into dimethylsiloxane. For example,
"Modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils described in technical data P6-18B, especially carboxy-modified silicone (trade name X-22-
3710) etc. are effective.

Also, JP-A-62-215953 and JP-A No. 63-46449.
The silicone oil described in this issue is also effective.

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. iiiImage formation accelerator promotes the redox reaction between silver salt oxidizing agent and reducing agent, promotes reactions such as generation of dye from dye-donating substance, decomposition of dye, release of diffusible dye, etc., and photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixing layer.
From a physicochemical function, it is a base or base precursor;
It is classified into nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Patent No. 4.
No. 678.739 No. 38-401III.

Examples of base precursors that can be used in heat-developable photosensitive materials include salts of organic acids and bases that are decarboxylated by heat;
These include compounds that release amines through intramolecular nucleophilic substitution reactions, Rossen rearrangement, or Beckmann rearrangement. Specific examples include U.S. Patent No. 4511.493 and Japanese Patent Application Laid-open No. 62-6
It is described in No. 5038 etc.

In a system in which development and dye transfer are performed simultaneously in the presence of water, it is preferable to include a base and/or a base precursor in the dye-fixing material in order to improve the storage stability of the light-sensitive material.

In addition to the above, there are also compounds that can react to form a complex with the sparingly soluble metal compounds and metal ions constituting the sparingly soluble metal compounds described in European Patent Publication No. 210.660 and U.S. Patent No. 4,740,445. Combinations of complex-forming compounds (referred to as complex-forming compounds) and compounds that generate bases by electrolysis as described in JP-A-61-232451 can also be used as base precursors. For example, the former method is effective.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, acid polymers or nitrogen-containing heterocyclic compounds,
Examples include mercapto compounds and their precursors. In addition, as materials that can be used in heat-developable photosensitive materials, acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with coexisting bases when heated, and more specifically, JP-A No. 6
No. 2-253159, pages (31) and (32).

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through rehearsal film or negative film using a printer or enlarger, and using a copy machine. A method in which the original image is scanned and exposed through a slit using an exposure device, etc., a method in which image information is transmitted via an electric signal to a light-emitting diode, various lasers, etc. for exposure, and a method in which direct image information is transmitted to a CRT, liquid crystal display, or electroluminescence. There is a method of outputting the image to an image display device such as a display or a plasma display and exposing the image directly or through an optical system.

As mentioned above, light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., such as U.S. Pat. No. 4,500,6.
The light source described in No. 26, No. 56451 can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, BaBzO, and other inorganic compounds,
Urea derivatives, nitroaniline derivatives, e.g. nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-5
Compounds described in No. 3462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. signal, CG, C
Image signals created using a computer such as AD can be used.

A method for processing a heat-developable photosensitive material will be described below.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
1-145544 can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50"C to about 250C, but a temperature of about 0C to about 180C is particularly useful. The dye diffusion transfer process is performed at the same time as the heat development. In the latter case, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular, the heating temperature in the transfer process is 50°C or higher. More preferably, the temperature is up to about 10° C. lower than the temperature in the development step.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 6123805
6, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 50
The temperature is preferably 50°C or more and 100°C or less when the solvent is water.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (particularly in mass sales, which is calculated by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating solution).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). It is also possible to use the solvent by incorporating it into the photosensitive material, the dye fixing material, or both in advance, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and melts at high temperature is incorporated into the light-sensitive material or dye fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or transfer process include contact with a heated plotter or plate, contact with a hot plate, hot presser, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. For example, it may be passed through a high-temperature atmosphere.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A-5975247, JP-A No. 59-177547, JP-A No. 59-181353, JP-A No. 6
Apparatuses described in Japanese Utility Model Application Publication No. 0-18951, Utility Model Application Publication No. 61-25944, etc. are preferably used.

Specific examples will be described below, but the present invention is not limited to these examples.

[Example 1] This section describes how to make photosensitive materials.

A well-stirred gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 6 ml of sodium chloride in 800 d of water)
(g and 301 g of the following chemical A were added and kept at 50°C), the following solutions (+) and (n) were simultaneously added at equal flow rates over 30 minutes. Then further below (Ill)
Solution and solution (IV) were added simultaneously over 30 minutes. Further, a solution of the following dye mixture was added 3 minutes after the start of addition of solutions (I[l) and (IV).

After washing with water, desalting, treating with lime, adding 22g of ossein gelatin to adjust the pH to 6.2 and PAg to 7.7, sodium thiosulfate and 4-hydroxy6-methyl-1,3,
Add 3a,7-chitrazaindene and chloroauric acid to 60°
Optimally chemically sensitized with C. In this way, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.38 μm was obtained. Yield was 635g.

Aggravating dye Aggravating dye Halon A well-stirred aqueous solution (730 af water to 22 g gelatin)
(0g of potassium bromide, 0.30g of potassium bromide, 6g of sodium chloride, and 0.015g of chemical A and kept at 60.0°C) were added with the following solutions (1) and (II) simultaneously over 30 minutes. Then, (I[[) solution and (IV) solution were mixed into 3
The solution of the sensitizing dye described below was added 1 minute after the addition was completed.

After washing with water and desalting, add 20 g of gelatin and adjust the pH. Triethylthiourea, chloroauric acid, 4-hydroxy-6-
Optimal chemical sensitization was performed using methyl-1,3,3a,7-chitrazaindene.

The emulsion obtained was a monodisperse cubic emulsion with an average grain size of 0.4 μm, and the yield was 630 g.

Optimal chemical sensitization was carried out by adding 6-methyl-1,3,3a, 7-chitrazaindene and chloroauric acid. In this way, 600 g of a monodispersed tetradecahedral silver iodobromide emulsion with an average grain size of 0.40 μm was obtained.

A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide, and 0.03 g of the following chemical A in 80 ml of water)
and HO(CHz)zs(CLhS(CHiLO)l
(0.25 g of the solution was added and kept at 50°C).To this, the following solutions (1) and (II) were added simultaneously over a period of 30 minutes. Thereafter, the following solutions (I[l) and (TV) were simultaneously added over 20 minutes. Further, after the addition of the solution (III) was completed, a solution of the following sensitizing dye was added for 5 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2, and after adding 8.5 G of PAg, sodium thiosulfate and 4-hydroxy-sensitizing dye (C) were added. 4503 (CHz)msOsH,NEts A method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 microns, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% aqueous gelatin solution. This was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm, and then the glass beads were separated to obtain a dispersion of zinc hydroxide.

A method for preparing an activated carbon dispersion will be described.

Activated carbon powder (reagent, special grade) manufactured by Wako Pure Chemical Industries ■ 2.5
g, 0.25 g of Demol NIg manufactured by Kao Soap ■ and polyethylene glycol nonyl phenyl ether as a dispersant were added to 100 - of a 5% gelatin aqueous solution, and the mixture was ground for 120 minutes using glass beads with an average particle size of 0.75 m in a mill. . The glass beads were separated to obtain an activated carbon dispersion with an average particle size of 0.5 μm.

A method for preparing a dispersion of an electron transfer agent will be described.

Add 10g of the electron transfer agent below, 0.5g of polyethylene glycol nonylphenyl ether as a dispersant, and 5g of the anionic surfactant IPIO below to a 5% aqueous gelatin solution, and mill glass peas with an average particle size of 0.75mm. was used for 60 minutes.

The glass beads were separated to obtain a dispersion of an electron transfer agent with an average particle size of 0.4 μm.

Electron transfer agent [phase] Anionic surfactant CHzCOOCl (zCH(CJs)C4HqNaOs
S C) How to make a gelatin dispersion of ICOOCHzCH(CzHs)CaHq dye-providing compound will be described.

Yellow, magenta, and cyan were each weighed according to the prescriptions in the table below, and each was heated and dissolved at about 60°C to form a uniform solution. 10% of this solution and lime-processed gelatin
100 g of the aqueous solution, 0.6 g of sodium dodecylbenzenesulfonate, and 50 Id of water were stirred and mixed, and then dispersed using a homogenizer at 110,000 rpm for 10 minutes. These dispersions are called gelatin dispersions of yellow, magenta, and cyan dye-providing compounds, respectively.

100 g of a 10% aqueous solution of ash-treated gelatin, 0.25 g of sodium bisulfite, 0.3 g of sodium dodecylbenzenesulfonate, and 30 d of water were stirred and mixed, and then dispersed using a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a gelatin dispersion of electron donor (1).

Dye-donating compound (1) Yellow dye-donating compound Next, a method of preparing a gelatin dispersion of the electron donor (2) for the intermediate layer will be described.

The following electron donor ■23.6g and the above high boiling point solvent ■8
．． Add 5g to 30d of ethyl acetate and dissolve by heating at 60°C.
A uniform i8 liquid was obtained. This/8 liquid and stone (2) Magenta dye-donating compound Cyan dye-donating compound Electron donor ■ Electron transfer agent Pre-forcer ■ High boiling point solvent ■ Electron donor ■ (Note 4) Antifogging agent ■ (Note 5 ) Surfactant ■ (Note 1) Surfactant ■ (Note 2) Surfactant ■ CH*C00CHzCB(CJs)Call*Na0s
S CHCOOCHzCH(Ctlls)CJw (Note 3) Water-soluble polymer (Note 6) Surfactant■ (Note 7) Hardener 0 1゜2-bis(vinylsulfonylacetamido)ethane 5S311 (Note 8) Antifoggant @ Next, we will discuss how to make the image-receiving material.

As shown in the following table, an image-receiving material (1) was prepared by coating the support (1) with the first layer and second layer of the back layer in a coating amount corresponding to the composition of the first to third layers. .

Here, how to make the third layer will be described in detail.

First, a 1% aqueous solution of kappa carrageenan was prepared.

500 methanol for 100g of copper carrageenan
After adding cc and stirring thoroughly, add 9 cc of 40℃ warm water.
After adding 500 cc, the liquid temperature was maintained at 60°C while increasing the temperature at a rate of 1°C/i, and the mixture was further stirred for 20 minutes.

Next, other chemicals were added in sequence. The liquid temperature after adding all chemicals was 55°C. During this time, the temperature of the inner wall of the dissolution tank was maintained at 60"C.

Next, keep the inner wall temperature of the dissolution tank at 18°C, and keep the liquid temperature at 4°C.
It was cooled to 0°C. When the liquid temperature reached 40°C, the temperature of the inner wall of the dissolution tank was set to 40°C.

During the process up to coating, the temperature of the wall surface of the manufacturing equipment that was in contact with the coating liquid was maintained at 45°C.

In addition, the coating liquid film thickness from the first layer to the third layer was 15%.
Coating was carried out using a simultaneous multilayer coating method using d/Bo, 40/I, and 15i/Bo.

After coating, a 10 m cooling zone at 20°C was set up,
Drying was performed using dry air at 30% RH.

Note that the gelation temperature of the third layer coating solution was 33°C.

Composition of image receiving material $4 (1) Structure of the support Silicone oil (1) C11゜ C.B.

Hz CH3 SiO-111-610)T-Ir-3iH3 (CHHz) , C0OH Hz (CH yo), □C0OH Surfactant (1) Surfactant (2) Water-soluble polymer (1) C@F+ 150. NCH2C00K Sumikagel L-5-H (manufactured by Sumitomo Chemical) C3H fu Water-soluble polymer (2) Surfactant (3) Dextran (Molecular weight 70,000) Mordant (1) CH.

Surfactant (4) zHs CHzCOOCHzCHCaHq High boiling point solvent (1) NaO,5 CHCOOCRZC)IC4H9 C2H3 Fluorescent brightener (1) Hardener (1) 2゜ 5-bis tertiary butyl benzio xazolyl (2)) Thiophene Surfactant (5) Matting agent (1) 1 C,H.

CBF,tsOJ-(CHzcHzo)a(CH
z) nsOJa benzoguanamine resin (average particle size I5μ
) Next, image-receiving materials (2) and (3) were prepared by changing only the method for preparing the 1% aqueous carrageenan solution of the third layer to image-receiving material (1) as follows.

The following treatments were carried out using the above-mentioned photosensitive material and image-receiving material.

That is, passing a gray wedge through the photosensitive material 101,
Exposure to tungsten light at 5000 lux l/10 seconds.

Next, while feeding this exposed photosensitive material at a linear speed of 20/sec, 15 d/n (water) is supplied to the mammary surface using a wire bar, and then the image-receiving material and film surface are immediately placed in contact with each other. The temperature was adjusted so that the temperature of the water-absorbed film surface was 85°C.Then, the image-receiving material (1) was heated in exactly the same manner as image-receiving materials (1) and (3) in Example 1.
-2a) and (3-2a) were created, respectively.

Next, use the same method as image-receiving materials (1-2a) and (3-2a) except for changing "maintain the inner wall temperature of the melting tank at 18°C" to "maintain the inner wall temperature of the melting tank at 26°C". Image receiving materials (1-2b) and (3-2b) were prepared respectively.

Next, a gray image was obtained in exactly the same manner as in Example 1, and each image-receiving material was evaluated for uneven white spots.

As is clear from the above results, the temperature of the wall surface in contact with the coating solution containing the water-soluble polymer of the present invention was determined using a gel roller.
When heated for 5 seconds and peeled off from the image receiving material, a clear gray image was obtained on the image receiving material.

The number of large and small circular white spots unevenness in this gray image was counted.

As is clear from the above results, when melting the water-soluble polymer of the present invention, by using water at a temperature of 5°C to 35°C as a solvent, the coated surface condition of the target object can be improved even in a short melting time. It is clear that there is a marked improvement regardless of the condition.

Example 2 The photosensitive material was prepared in exactly the same manner as in Example 1.

It is clear that the condition of the coated surface of the target object is significantly improved by maintaining the coating temperature above -10°C. On the other hand, the inner wall temperature of the melting tank is "gelling temperature (℃) +
In the manufacturing method of the coating liquid in which the temperature is maintained at 40° C. or higher, that is, 73° C. or higher, the manufacturing time becomes long and reactions occur in the coating liquid.

Claims (3)

[Claims] (1) In a method for producing a coating solution containing a water-soluble polymer that undergoes reversible sol-gel conversion by heating and cooling an aqueous solution, when dissolving the water-soluble polymer, 5°C or more and 35°C
A method for producing a coating liquid, which comprises adding and dissolving the following water as a solvent. (2) Manufacturing a coating solution containing a water-soluble polymer that undergoes reversible sol-gel conversion by heating and cooling an aqueous solution, and manufacturing equipment that comes into contact with the coating solution throughout the entire process until it is coated on a support. Set the temperature of the wall surface to ``gelation temperature (℃) of the coating liquid - 10℃'' or higher ``gelation temperature (℃) + 40℃''
2. The method for producing a coating liquid according to claim 1, wherein the method is as follows. (3) The method for producing a coating liquid according to claim 1 or 2, wherein the water-soluble polymer is a natural polymeric polysaccharide selected from agar, kappa carrageenan, lambda carrageenan, iota carrageenan, and furseleran.